US3679481A - Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells - Google Patents

Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells Download PDF

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Publication number
US3679481A
US3679481A US119867A US3679481DA US3679481A US 3679481 A US3679481 A US 3679481A US 119867 A US119867 A US 119867A US 3679481D A US3679481D A US 3679481DA US 3679481 A US3679481 A US 3679481A
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US
United States
Prior art keywords
carrier
nickel
cadmium
hydroxide
oxide
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Expired - Lifetime
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US119867A
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English (en)
Inventor
Emile Jean Lucien Pinard
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SAFT Societe des Accumulateurs Fixes et de Traction SA
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SAFT Societe des Accumulateurs Fixes et de Traction SA
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/24Electrodes for alkaline accumulators
    • H01M4/26Processes of manufacture
    • H01M4/28Precipitating active material on the carrier
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the resultant negative electrode has a materially reduced amount of deleterious or parasitic positive active material and increased porosity and flexibility as compared with like negative electrodes produced by conventional carrier impregnating and precipating procedure.
  • Negative electordes resulting from the process of this invention and alkaline storage cells with such negative electrodes are also disclosed.
  • This invention relates to improvements in the manufacture of negative electrodes comprising sintered porous metallic carriers bearing active negative material intended for use in alkaline storage cells and more especially to the manufacture of negative electrodes whose active negative material is a cadmium compound such as cadmium hydroxide and which are particularly useful in sealed cells.
  • the invention also relates to the electrodes resulting from the method of this invention and to electrochemical storage cells containing such electrodes.
  • the conventional manufacturing method for negative electrodes whose active material is cadmium hydroxide consists in impregnating a sintered porous nickel carrier with a solution of a cadmium salt, preferably cadmium nitrate which is slightly acidified, e.g. by nitric acid, into which the carrier is immersed or dipped, then in immersing the thus impregnated carrier in an alkaline solution e.g. of potassium hydroxide or preferably sodium hydroxide, preferably at high temperature in order to precipitate cadmium hydroxide in the pores of the carrier. This procedure is usually repeated several times until a suitably selected amount of cadmium hydroxide has been deposited in the pores of the sintered carrier.
  • a cadmium salt preferably cadmium nitrate which is slightly acidified, e.g. by nitric acid
  • This phenomenon may occur at the end of the discharge in the cell having the smallest capacity among the cell of a battery.
  • Objects and features of the present invention are to remedy these drawbacks and make possible the manufacture of sintered carrier type negative electrodes that are substantially free of undesired positive active materials without at the same time introducing any other impurities.
  • the heating step is effected at a temperature of about 250 C. for a period of about one hour.
  • the nickel oxide and cadmium oxide bearing electrode carriers are submitted to a rehydrating step and finally washed and dried.
  • the rehydrating step comprises immersion of the nickel oxide and cadmium oxide bearing porous carriers in a heated aqueous liquid such as pure (distilled) water maintained at a temperature of about 80 C. or more preferably a dilute aqueous solution of nickel sulfate at a concentration advantageously of about 2.5 g./l. alsomaintained at said temperature of about 80 C. or alternatively in a sodium hydroxide solution at a concentration advantageously of about 250 g./l. also maintained at said temperature of about 80 C.
  • the immersion in the selected heated aqueous liquid may be maintained for from approximately 1 to approximately 2 hours.
  • practice of the processaccording to the invention has an additional advantage in that it facilitates the elimination of residual nitrates remaining in the product resulting from the two conventional preliminary conventional impregnation and precipitation steps by simple washing because such nitrates are thus made soluble, so that the usually required electrochemical purification procedure of electrodes produced by the conventional impregnation and precipitation steps only and consisting in cathodically and anodically polarizingsuch electrodes in an alkaline solution in order to rid them of their impurities, which usually follow the impregnation and precipitation steps of the conventional method becomes unnecessary.
  • the negative electrodes produced in accord with the practice of the method of the invention present an increased flexibility over the electrode product of the said conventional method. This is very advantageous especially when such electrodes are to be used for manufacturing cells with wound electrodes.
  • the flexibility of electrodes resulting from conventional impregnation and precipitation procedure (which may be tested by the deflection of a resulting electrode held at one end and submitted at the other end to an increasing load) is doubled by the subsequent electrochemical purifying procedure hereinabove mentioned as compared with an electrodewhich has not been so purified, I have found that this flexibility is increased three times in electrodes prepared according to the method of this invention employing the said heating step at 250 C. followed by a rehydration step in a sodium hydroxide solution.
  • Negative electrodes prepared according to this invention are therefore advantageous because of their superior 4 porosity, flexibility and relative freedom of presence of active positive materials in substantial and deleterious amounts as well as freedom from other impurities.
  • a band or strip of porous sintered nickel carrier material in conventional manner is immersed in an acidified salt solution of the desired active material, for example, a solution of cadmium nitrate to impregnate its pores, followed by immersion in an alkaline solution, for 'example, of sodium hydroxide at elevated temperature to precipitate cadimum hydroxide in the pores of the carrier, this precipitation being accompanied, too, by precipitation into the carrier pores of the nickel from the carrier which has been attacked by the impregnation solution and its conversion into nickel hydroxide by said alkaline soluton, said two immersion steps being repeated as needed for several times in seriatim until a desired quantity of cadmium hydroxide deposit has been effected in the pores of the carrier accompanied, of course, by precipitation of parasitic and'undesirable nickel hydroxide from the nickel of the carrier.
  • an acidified salt solution of the desired active material for example, a solution of cadmium nitrate to impregnate its pores
  • the precipitate bearing carrier product of these impregnation and precipitation steps is then washed and dried and further subjected to a heating step in air at about 250 C. for about one hour to etfect conversion of the precipitated nickel hydroxide and cadmium hydroxide into nickel oxide and cadmium oxide.
  • a rehydration step is effected by immersion of the nickel oxide and cadmium oxide bearing carrier product of said heating step in an aqueous nickel sulfate solution having a concentration of about 2.5 g./l. maintained at a temperature of about C.
  • Example II The procedure of Example I is followed with a similar 7 pregnating and precipitating procedure and with a further,
  • Alkaline storage cells utilizing negative electrodes resulting from the practice of this invention may be assembled together with suitable positive electrodes and interposed separators and with conventional alkaline electrolytes.
  • the electrode-separator assemblies may be spirally wound, if desired, and in all event enclosed in appropriate sealed containers in known manner.
  • Negative electrodes resulting from the practice of this invention are highly porous and flexible and comprise a sintered porous nickel carrier whose pores include as active negative material finely divided cadmium hydroxide and also include some inert nickel oxide as impurity but are substantially free of other impurities.
  • That improvement in the process of manufacturing a negative electrode for alkaline storage cells comprising the steps of providing a porous nickel carrier, impregnating pores of the carrier with a cadmium salt solution, then precipitating cadmium hydroxide in said pores accompanied by precipitation of some nickel hydroxide from attached nickel of the carrier by immersion of the impregnated carrier in an alkaline solution, subsequently washing and drying the multi-hydroxide bearing carrier, heating the multi-hydroxide bearing carrier after said drying to a temperature ranging from 200 C. to 500 C.
  • aqueous liquid is nickel sulfate solution having a concentration of approximately 2.5 g./l. 6. That improvement in the process of manufacturing a negative electrode for alkaline storage cells according to claim 1 wherein said aqueous liquid is a sodium hydroxide solution having a concentration of approximately 250 g./l.
  • said porous metallic carrier is a band or strip of 'sintered nickel, wherein said metallic salt solution is an acidified cadmium nitrate solution, wherein said alkaline solution is an alkali metal hydroxide solution, wherein said first-named metallic hydroxide is cadmium hydroxide and said second-named hydroxide is nickel hydroxide and wherein said aqueous liquid for said rehydration is selected from the group consisting of water, nickel sulfate solution and sodium hydroxide solution.
  • the duration of said rehydration is from approximately 1 to approximately 2 hours.
  • aqueous liquid is a sodium hydroxide solution having a concentration of approximately 250 g./l.
  • That improvement in the process of manufacturing 8 a a negative electrode for an alkaline storage cell comprising the steps of providing a porous sintered nickel carrier strip, immersing said strip in an acidified cadmium nitrate solution to impregnate pores of said carrier strip, then immersing the so-impregnated carrier strip into an alka-.
  • aqueous solution is sodium hydroxide at a concentration of 250 g./l. and the last-named drying is etfected in decarbonated air.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US119867A 1970-03-26 1971-03-01 Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells Expired - Lifetime US3679481A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7010933A FR2082771A5 (fr) 1970-03-26 1970-03-26

Publications (1)

Publication Number Publication Date
US3679481A true US3679481A (en) 1972-07-25

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US119867A Expired - Lifetime US3679481A (en) 1970-03-26 1971-03-01 Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells

Country Status (9)

Country Link
US (1) US3679481A (fr)
AU (1) AU2699071A (fr)
BE (1) BE764139A (fr)
CA (1) CA981332A (fr)
DE (1) DE2106130A1 (fr)
FR (1) FR2082771A5 (fr)
GB (1) GB1279587A (fr)
LU (1) LU62751A1 (fr)
NL (1) NL7104066A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032697A (en) * 1974-05-20 1977-06-28 Bell Telephone Laboratories, Incorporated Methods of producing electrodes for alkaline batteries
US4139423A (en) * 1978-04-07 1979-02-13 General Electric Company Sintered negative plate
US4166010A (en) * 1978-04-07 1979-08-28 General Electric Company Sintered negative plate
US5401460A (en) * 1993-11-23 1995-03-28 M-C Power Corporation Method for sintering fuel cell electrodes using a carrier
US5833452A (en) * 1994-12-15 1998-11-10 M-C Power Corporation Coated metal sintering carriers for fuel cell electrodes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2343595C1 (ru) * 2007-10-22 2009-01-10 Иршат Атауллович Махмутов Способ изготовления безламельного кадмиевого электрода

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032697A (en) * 1974-05-20 1977-06-28 Bell Telephone Laboratories, Incorporated Methods of producing electrodes for alkaline batteries
US4139423A (en) * 1978-04-07 1979-02-13 General Electric Company Sintered negative plate
US4166010A (en) * 1978-04-07 1979-08-28 General Electric Company Sintered negative plate
US5401460A (en) * 1993-11-23 1995-03-28 M-C Power Corporation Method for sintering fuel cell electrodes using a carrier
US5833452A (en) * 1994-12-15 1998-11-10 M-C Power Corporation Coated metal sintering carriers for fuel cell electrodes

Also Published As

Publication number Publication date
GB1279587A (en) 1972-06-28
LU62751A1 (fr) 1971-08-23
NL7104066A (fr) 1971-09-28
CA981332A (en) 1976-01-06
FR2082771A5 (fr) 1971-12-10
DE2106130A1 (de) 1971-10-14
BE764139A (fr) 1971-09-13
AU2699071A (en) 1972-09-28

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